Optical brightening and new compositions of matter



United States Patent 3,400,124 OPTICAL BRIGHTENING AND NEW COMPOSITIONS OF MATTER Ichiro Okubo and Michihiro Tsujimoto, Tokyo, Japan, assignors to Mitsui Kagaku Kogyo Kabushiki Kaisha, Chuo-ku, Tokyo, Japan No Drawing. Continuation-impart of application Ser. No. 220,904, Aug. 31, 1962. This application May 18, 1966, Ser. No. 550,957

Claims priority, application Japan, Sept. 12, 1961, 36/243,302; July 18, 1962, 37/29,641 8 Claims. (Cl. 260-240) ABSTRACT OF THE DISCLOSURE The invention described in this specification is concerned with new compounds having highly outstanding optical properties which render them useful in a variety of environments as optical brighteners. The new compounds are chemically defined as styrylnaphthoxazoles, especially outstanding members of the groups being those which contain substituents on the styryl grouping, for example, halogen, cyano, or both. The optical activity may be employed to advantage in a wide variety of different uses; however, they are especially useful in the brightening of fabrics.

This application is a continuation-in-part of our prior applications Ser. No. 220,904, filed Aug. 31, 1962, now Patent No. 3,262,929, and Ser. No. 502,414, filed Oct. 22, 1965, now Patent No. 3,347,694.

This invention relates to improvements in the field ofv CROSS KL 3,400,124 Patented Sept. 3, 1968 naphthoxazoles temperature-stable, but they may be employed in the presence of other material commonly included as brightening compositions, e.g. hypochlorite, without impairment. The said naphthoxazoles may be included as a component of polymer melts and processed therewith to products of whatever variety, thereby providing their brightening effects in such products. Similarly the said naphthoxazoles may be applied by way of solution to the surface of solid products of polymeric substrates.

As indicated above, the said naphthoxazoles may be applied to a wide variety of materials including wool, silk, cotton and to various synthetic materials. Their general applicability is therefore quite exceptional when compared to other known brighteners. Also, their stability renders them highly unusual. Further, as indicated above, the" said naphthoxazoles may be applied to the various materials regardless of their form; however, they are especially important and useful in the treatment of natural organic fibrous and synthetic filamentary materials. Materials treated according to this invention are rendered excellently light fast.

From the foregoing, it will be appreciated that the new materials of this invention are outstanding in many respects in addition to their intrinsic brightening power, which will be seen more fully hereinafter. Moreover, as will appear, certain of the said naphthoxazoles are superior to others and also as regards their efiectiveness on particular substrates.

The novel Z-styrylnaphthoxazole compounds of this invention have the structure represented by the general formula:

wherein A is an unsubstituted naphthalene ring, which is condensed with the oxazole ring, and R and R' are selected from hydrogen, halogen, cyano grou carboxyl group and its ester residue, alkyl group and aryl group,

Examples of novel 2-styrylnaphthoxazole compounds of this invention are shown below in Table I.

TABLE 1 Fluores- No. Structural Formula Property and cence in me ting point benzene Solution O Colorless flake- Blue-violet.

like crystals Mi C /C-CH=HC N Slightly yellow Blue.

pillar-like CCH=HC crystals 134- 135 C. N

Lmmuun TABLE 1-C0ntinued No. Structural Formula o 7 c-cH=Hc-F C-CH=HCBr g}; o 9 c-cn=nc cn.

CCH=HCCOOH Fluores Property and cence in melting point benzene o solution Light-yellow Green-blue.

pillnr-like crystals 122l23 C.

Slightly yellow Blue-green.

needleike crystals 158-159" C.

Light yellow Blue.

flake-like crystals 114-115" C.

Yellow needle Green-blue.

like crystals 159-160 C.

Light yellow Violetpillar-like blue. crystals 125l26 C.

Light yellow flake-like crystals 123-124" C Violetbluei Yellow long flake-like crystals 300 0 Blue.

The preparation of the said naphthoxazoles is described in our said prior application Ser. No. 220,904 filed Aug. 31, 1962, now Patent No. 3,262,929, to which reference may be had in this connection. The novel 2- styryinaphthoxazole compounds herein described can be prepared by 75 condensation under dehydration of an a-methylnaphthoxazole compound with benzaldehyde or a derivative thereof wherein the benzene ring contains substituents as defined hercinabove in connection with Formula I. This condensation reaction can be carried out by mixing both of the said starting materials at about equal molar ratio and heating them at about 150-200 C. If desired, a dehydrating agent may be employed. The reaction usually re- 6 ing Conditions and the light-fastness (according to Japanese Industrial Standard Ll045-l959, xenon light source) in this case are shown in Table 2.

quires several hours, water being removed as necessary. The reaction product is recovered by dissolving in a suitable solvent, -for example, methanol, followed by crystallization therefrom, suitably followed by recrystallization.

As shown in Table l, the novel 2-styrylnaphthoxazole compounds used according to this invention are soluble in the organic solvent and the solutions exhibit strong fluorescence of blue violet to violet in day-light and in ultra violet light.

The organic fibrous materials to be treated by the process of this invention can include natural fibres such as silk and wool, and man-made fibres. It is particularly remarkable that brightening effect is superior on the man-made fibrous materials such as polyester, polyacrylonitrile, polyamide, acetalized polyvinyl alcohol and polyolefin and cellulose acetate fibres, and light fastness on these materials is excellent.

The treatment of the various fibrous materials under the process of this invention can be carried out according to the well known dyeing process, which is common in the case of the disperse dye, for instance, the novel 2- styrylnaphthox-azole compounds are dispersed in water by addition of surface-active agents and the fibrous materials are immersed in the prepared dispersed system. As available surface-active agent, there are either anionic or nonionic compounds such as alkyl benzene sulfonic acid and the condensation product of naphthalene sulfonic acid and formaldehyde or polyoxyethylenealkylether and the like.

The treatment temperature in the dispersed system may vary between 50 C. and 130 C. depending on the kind of the fibrous materials to be treated.

It is of advantage when the textile materials of polya ester fibre are treated by the above process to add a carrier such as trichlorobenzene or methylsalicylate in the bath, as the brightening effect can be much improved.

It is also of particular advantage, especially when the textile materials of polyester or blended fabrics of polyester and cotton are treated in the form of fabrics, to apply the dry heating at between 160 C. and 220 C. for a time in the range of 2 to 0.5 minutes, according to the so-called thermosol process.

According to the process of this invention, it is also possible for the optical brightening of the man-made fibrous materials to add the said compound to spinning mass before the spinning thereof.

The amount of the novel 2-styrylnaphthoxazole compounds to be used according to the invention is preferably between 0.02% and 0.4% based on the weight of material to be treated.

The compound No. 5 in Table I is made into aqueous dispersed system by using an anionic surface-active agent of alkylbenzenesulfonic acid type, and when the abovementioned man-made fibres are treated in a treating bath which is prepared in such a way as the amount of this compound is 0.1% or 0.2% to the weight of the mate rials to be treated, an excellent optical brightening effect can be obtained as to each of the fibres. The treat EXAMPLE 1 One part of 2-(3-chlorostyryl)-fl-naphthoxazole of the formula is thoroughly mixed with 9 parts of surface-active agent of alkylbenzene sulfonic acid type to give a sample, and 0.1 part of the sample thus prepared per 10 parts of cellulose acetate fabrics to be treated is put into 400 parts of water to give an aqueous dispersion. In this aqueous dispersion the cellulose acetate fabrics are treated at C. for 45 minutes. The treated fabrics are washed with water and dried. A remarkable brightening effect is obtained as compared with non-treated fabrics.

EXAMPLE 2 When nylon fabrics or Vinylon, acetalized polyvinyl alcohol fabrics, are used in place of acetate fabrics in Example 1, a remarkable brightening effect similar to Example l is obtained.

EXAMPLE 3 When polypropylene yarn is used in place of acetate fabrics in Example 1 and treated at 100 C., a remarkable brightening effect similar to Example 1 is Obtained.

EXAMPLE 4 0.1 part of the sample prepared in Example 1 is added to 400 parts of water to prepare an aqueous dispersion. To this dispersion is added 0.2 part of formic acid and then 10 parts of Vonnel W, polyacrylonitrile fabric is treated in this bath liquid at C. for 45 minutes. The treated yarn is washed with water and dried. A remarkable brightening effect similar to Example 1 is obtained.

EXAMPLE 5 When polyester fabrics is used in place of acetate fibres in Example 1 and treated at C., a remarkable brightening effect similar to Example 1 is obtained.

7 EXAMPLE 6 When Z-styryI-fi-naphthoxazole of the formula is used in place of 2-(3'-chlorostyryl)-;9-naphthoxazole in Example 5, a remarkable brightening effect is obtained.

EXAMPLE 7 A concentrated suspension is previously prepared by mixing 1 part of 2-(4-chlorostyryl)-fi-naphthoxazole of the formula /0 l CH=HC C.

2 parts of the surface-active agent of polyoxyethylenealkylether type and 7 parts of water.

A bath liquid is prepared by diluting the above concentrated suspension so as to make the concentration of the 2-styrylnaphthoxazole compound to be 0.2%. Tetoron polyester fabrics are immersed in the bath at room temperature, then squeezd out to a liquid content of 50%, dried at room temperature and subjected for 60 seconds to a further heat treatment in an air bath which is kept at 200 C. The fabrics are washed in hot soap solution and rinsed. The dried fabrics are particularly brightened as compared with the untreated materials.

As indicated above, the compounds of the present invention differ in their effectiveness. For example, referring to Table 1 compound No. is found to be greatly superior to compound No. 3, especially in the treatment of spun polyester cloth. The difierence may be clearly perceived with the naked eye. Table 3 below sets forth data in this connection.

TABLE 3.COMPARISON OF BRIGHTENING EFFECTS ON SPUN POLYESTER CLOTHS Treatments 1 Compound N o. 3 Compound No. 5

l Specific fluorescent intensity of the treated cloths. Amount percent of brightener used (0.1K. fibre).

The treatments involved in Table 3 were carried out as follows:

500 mg. of fluorescent brightener were dispersed in 100 ml. of dimethylformamide, and 50 ml. of the resultant solution were poured into 450 ml. of 1% aqueous solution of polyoxyethylenealkylether-type nonionic surfactants under stirring, and the mixture was kept as the stock solution. Using 5 ml. or ml. of the stock solution, 250 ml. of the treating liquid (bath) containing 500 mg. of sodium alkylbenzenesulfonate-type surfactant was prepared, and in the said treated solution 5 g. of spun polyester cloths were treated at 100 C. and 120 C. for 40 minutes.

The treated cloths thus obtained were washed with water and then air dried.

TABLE 4.COMPOSITION OF HEAVY DUTY DETEBGENTS Components: Composition in percent Sodium alkylbenzene sulfonate 33.0 Sodium tripolyphosphate 31.0 Sodium silicate 5.0 CMC (carboxymethylcellulose) 0.8 Sodium sulfate 30.2

Treating liquids (liquor ratio 1:50) containing 1% O.W.F. of compound No. 3 were prepared to provide 0.25 and 5 g./liter of heavy duty detergent.

Unbleached muslin and nylon-taffeta were treated one and five times by each fresh bath (liquid), and washed with water. After air-drying, the relative fluorescent intensities were determined.

The Launder-Ometer (having ten steel balls, 42 r.p.m.) was employed for the treatments and the experiments were carried out at 40 C. for 30 minutes. Excellent brightening effects are provided, especially in the treated nylon cloths.

The other compounds herein disclosed may be similarly applied in detergent compositions.

What is claimed is:

1. A 2-styrylnaphthoxazole compound represented by the following formula:

wherein A is an unsubstituted naphthalene ring, which is condensed with the oxazole ring, and wherein R and R are different substituents, at least one of which is selected from halogen, cyano group, carboxyl group and its lower alkyl ester residue, lower alkyl alkyl group and phenyl group.

2. A compound as claimed in claim 1 wherein said R is halogen.

3. A compound as claimed in claim 1 wherein said R is chlorine.

4. 2-(3-chlorostyryl)-fl-naphthoxazole having the following formula:

5. 2-(4'-chlorostyryl)-fi-naphthoxazole having the following formula:

6. 2-(3-chlorostyry1)-a-naphthoxazole having the f0llowing formula:

C-CH=CH 10 7. 2-(2'-chlorostyryl)-u-naphthoxazole having the fol- 15 lowing formula: 3 274 184 8. 2-(4-fiuorostyry1)-p-naphthoxazo1e having the following formula:

References Cited UNITED STATES PATENTS 1/ 1944 RieSter 260-240 7/1966 Okubo et a1 260240 9/1966 Thompson 260240 FOREIGN PATENTS 6/1959 Canada.

1 OTHER REFERENCES 0 C1 Beilsteins Handbuch der Organische Chemie, vol. 27, 4th ed. Main Work. pages 83-84 (System #4203) (1937), QD241B5. 25

JOHN D. RANDOLPH, Primary Examiner. 

